Water resisting and anticorrosive paint vehicle

ABSTRACT

A paint vehicle comprising a hydrocarbon compound having a specific gravity of from 0.92 to 1.0, a mean molecular weight of from 200 to 1000 measured by a vapor pressure osmotic pressure method, an aromatic C-H proton density of less than 3 percent, said aromatic C-H proton having a Tau value of less than 4 determined by nuclear magnetic resonance absorption spectrum, and a transparency such that the percent transmittance of a 10 percent hexane solution thereof, measured by the absorption of visible light of wavelengths longer than 500 m Mu , is higher than 60 percent.

United States Patent 1 Enomoto et al.

WATER RESISTING AND ANTICORROSIVE PAINT VEHICLE lnventors: Satoru Enomoto; Hisayuki Wada; Mikio Fujioka; Masao Koguro, all of Fukushima, Japan Assignee: Kureha Kagaku Kogyo Kabushiki Kaisha, Tokyo, Japan Filed: July 23, 1970 Appl. No.: 57,666

Foreign Application Priority Data July 23, 1969 Japan ..44/S7625 US. Cl. ..208/l4, 208/44, 260/667, 260/671 G, 260/33.6

Int. Cl. ..Cl0g 39 00 Field of Search ..208/l4, 49, 62, 143, M4, 22, 208/44; 260/667 51 Jan. 30, 1973 [56] References Cited UNITED STATES PATENTS 2,9l0,426 l0/l959 Gluesenkamp et al. ..208/l43 Primary ExaminerHerbert Levine Attorney-Sughrue, Rothwell, Mion, Zinn and Macpeak [57] ABSTRACT A paint vehicle comprising a hydrocarbon compound having a specific gravity of from 0.92 to 1.0, a mean molecular weight of from 200 to 1000 measured by a vapor pressure osmotic pressure method, an aromatic C-H proton density of less than 3 percent, said aromatic C-H proton having a 1 value of less than 4 determined by nuclear magnetic resonance absorption spectrum, and a transparency such that the percent transmittance of a 10 percent hexane solution thereof, measured by the absorption of visible light of wavelengths longer than 500 mg, is higher than 60 percent.

2 Claims, 3 Drawing Figures AROMATIC C-H PROTON DENSITY PAIENTEDJAI30 1975 FIG] lll

I III II I II w 7 rr 1 I0 800 900 INVENTORS SATORU ENOMOTO HISAYUKI WADA, MIKIO IfUJIOKA,MASAO KOGURO ,M. *MPQK ATTORNEYS 400 420 440 460 480 500 550 600 650 700 WAVE LENGTHS AND ANTICORROSIVE PAINT VEHICLE BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel paint vehicle, the vehicle comprising a naphthenic compound which is almost colorless and transparent and one which has water resisting and anticorrosive properties.

2. Description of the Prior Art In general, resins having so-called three-dimensionally cross-linked structures, such as alkyd resins, epoxy resins, urethane resins, etc., have been known to have excellent properties as coating materials but since they are insufficient in water resisting and anticorrosive properties, it has been strongly desired to improve such properties. On the other hand, from the viewpoint of application of painting materials, the development of a paint vehicle which can be painted as thick as possible by one painting operation has also been strongly desired in this field.

Hitherto, as materials for satisfying both of the above demands, coal tar and coal pitch have been employed as paint vehicles. However, coal tar and coal pitch have such faults that since they are black, the use thereof is limited to a narrowed range and also it is quite difficult to supply thesematerials having constant qualities successively. Furthermore, since impurities originating from the coal used as the raw material inevitably occur in the vehicle, the stability during preservation is WATER RESISTING reduced and also they give off specific odors, which in turn results in various disadvantages from the aspects of working properties and sanitation. Moreover, a painting material containing coal tar or coal pitch has the further disadvantage that when the coating material is practically applied and subjected to outdoor expo sure for a long period of time, the gloss of the coating is degraded, a chalking phenomenon occurs, and the mechanical properties are greatly reduced.

Therefore, a principal object of the present invention is to provide a paint vehicle which can provide to the paint such advantages as a high water-resisting property, a suitable anticorrosive property and thick paintability.

SUMMARY OF THE INVENTION The present invention provides a paint vehicle comprising hydrocarbon compounds having the following characteristics:

a. a transparency such that the present transmission of a 10 percent hexane solution thereof, measured by the absorption of visible light of a wavelength longer than 500 mg, is higher than 60 percent;

b. a mean molecular weight of from 200 to 1,000,

' measured by a vapor pressure osmotic pressure method (hereinafter referred to as the VP0 method);

c. a specific gravity of 0.92 to 1.0; and

d. an aromatic CH proton density of less than 3 percent, determined by means of a high resolving power, nuclear magnetic resonance absorption spectrum (wherein the 7 value of tetramethylsilane is defined to be. 10 as a standard, a 1' value less than 4 is the aromatic CH proton, and a value of 4 to 10 is the alkyl chain proton and the methylene proton), hereinafter referred to as NMR. See

FIGS. 1 and 2 for a graphic analysis of the aromatic CH proton density requirement.

From the results of measurements by various analytical means and the results of measuring physical properties, the hydrocarbon compounds of the present invention are assumed to be composed of a group of compounds in which an alkyl group having less than eight carbon atoms, and preferably less than four carbon atoms, has been added to a compound having at least two naphthene rings combined in linear fashion, a compound wherein at least two naphthene rings have been condensed, or a compound wherein single ring naphthenic compounds have been linearly combined. However, since an overall conclusive analysis of the hydrocarbon compounds of the present invention cannot be performed, the compositions of the hydrocarbon compounds have not yet been confirmed. Therefore, as a measure of the naphthene rings which are the prin cipal features of the vehicle of this invention, the presence of aromatic rings by measuring the NMR is limited to the procedure as described above (i.e., the percentage of the aromatic CH proton density).

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing the NMR spectrum of the vehicle of the present invention;

' FIG. 2 is a graph showing the NMR spectrum of a substance having an aromatic CH proton density higher than 3 percent, which is outside the scope of this invention; and

FIG. 3 is a graph showing the visible spectrum of both the vehicle of this invention and the substance characterized in FIG. 2.

DETAILED'DESCRIPTION OF THE PREFERRED EMBODIMENTS As is clear from the results shown in FIG. 3, curve 2, the substance shown in FIG. 2, is colored.

Also, the vehicle of this inventionis utterly different from alkylnaphthenic compounds such as liquid paraffin; in particular, the former has a larger specific gravity and is more compatible with resins than the latter. This is astonishing when it is considered that liquid paraffms show less of a miscibility with resins as additives for coating compositions.

The degree of transparency of the vehicle of this invention when shown by the Gardner color number is less than 8, and this is so defined in this invention that the percent transmittance of a solution prepared by dissolving l0 g of the vehicle of this invention in 100 ml of hexane or tetrahydrofuran, measured by the absorption of visible light of wavelengths longer than 500 mg, is higher than 60 percent, and preferably higher than percent. This is also clearly confirmed by thefact that the vehicle is colored by increasing the proportion of the aromatic C- I-I protons of the aromatic rings as shown in FIGS. 1-3. Also, it is preferable that the softening point of the vehicle of this invention be in a range of 25l00 C as a solid and the viscosity thereof as a liquid at 25 C be l,00050,000 cps.

The aforesaid vehicle of the present invention is colorless and transparent but may be colored by coloring materials such as pigments, etc.

Furthermore, the vehicle of this invention has no bad odor as does coal tar, etc., and has very few aromatic rings in its structure, and thus, the vehicle is harmless to both humans and animals and also has no bad influences on the work property of the paint. In addition, it also has a sufficient compatibility with resins, water resisting property, weathering resisting property, anticorrosive property and a thick paintability. Therefore, the vehicle of the present invention overcomes the above-mentioned disadvantages without losing the merits of coal tar or coal pitch.

The vehicle of this invention may be prepared by hydrogenating the aromatic rings of hydrocarbon compounds containing a large amount of aromatic rings (i.e., more than two rings). As such hydrocarbon compounds, there are illustrated coal tars, various residual oils obtained in petroleum refining treatments (e.g., v

visbraker residual oil, coker residual oil, catalytic cracking cycle oil, dealkylation residual oil, etc.), high temperature cracked residual oils of petroleum (e.g., bottom oil recovered during the production of ethylene by the cracking of naphtha, tars recovered during the production of ethylene-acetylene, and oil tars byproduced by the high temperature gasification cracking of petroleum crude oil, heavy oil, etc.), and the like.

Moreover, for improving the flexibility and compatibility in the painting properties of the vehicle, it is possible as the case may be to conduct the nucleus hydrogenation of the feed stock after alkylating the aforesaid hydrocarbons with olefins having less than eight carbon atoms, preferably less than four carbon atoms. The nucleus hydrogenation may be conducted using a catalyst and apparatus employed for ordinary hydrogenation processes. in this case, however, it is preferable to conduct, before the hydrogenation, a desulfurization step, which is generally used for removing impurities which may poison the catalyst.

The desulfurization may be conducted in a conventional manner using a known desulfurization apparatus. The catalyst to be employed in the desulfurization step involves cobalt, molybdenum or nickel in the form of metals, oxides, sulfides, or combinations thereof which may be supported by suitable carriers such as alumina and silica-alumina. The desulfurizing reaction is carried out at a temperature of 350 to 450 C under a pressure of 20-100 kg/cm using a feed ratio (molar ratio of hydrogen to tar fraction) of 3-20 moles/mole, at a liquid hourly space velocity of 0.5- cc/cc-cat/hr (L.H.S.V.). Under such conditions, the reaction takes place readily to attain good desulfurization of the sulfur contained in the tar fractions.

The subsequent alkylation reaction is conducted by mixing the gaseous olefins with the tar fraction and reacting them in the presence of a suitable catalyst. The catalyst to be employed preferably includes a silica-alumina type catalyst or a metal belonging to Group Ill-B of the Periodic Table, such as lanthanum, cerium, thorium, etc., carried by a suitable carrier such as zeolite.

The feed olefin to be used is preferably a lower olefin generally having not more than eight carbon atoms, preferably two to four carbon atoms. Typical olefins to be used are ethylene, propylene, butylene. The use of such olefins is economically advantageous. The reaction conditions to be employed are as follows: a temperature between 150 C and 380 C, a pressure between 1 and 50 kg/cm a feed ratio between 0.2 and 10 moles of olefin per mole of the tar fraction and a liquid hourly space velocity of from 0.1 to 50 cc/cccatalyst/hr.

The reaction takes place readily with the use of the catalyst and is conducted over a prolonged period of time without decrease of the activity of the catalyst.

Since the tar fractions have very few side chains, an alkyl side chain may be added under desired control. The length of the alkyl group to be added depends upon the kind of olefin to be used and the degree of alkylation (the moles of olefin to be reacted per mole of the tar fraction) can be increased by employing a high feed ratio or by employing a small liquid hourly space velocity. The alkylated tar thus formed has a lower specific gravity and refractive index as well as a higher H/C, viscosity, average molecular weight and boiling point than those of the feed tar fraction. Through analysis of the alkylated product by means of gas chromatography, infrared absorption spectrum or nuclear magnetic resonance absorption spectrum, etc., the alkylated tar is estimated to have a chemical structure consisting of condensed polycyclic aromatic rings having from two to five, preferably from two to four, aromatic rings which are combined with added alkyl groups having the same carbon number as that of the olefin used in the reaction.

The subsequent hydrogenation reaction is carried out by admixing the alkylated tar with hydrogen and reacting them in the presence of a suitable catalyst. The

catalyst to be used in the hydrogenation process includes the metals belonging to Groups VI, VII, and VIII, and oxides and sulfides thereof, and combinations of them. These components may be supported by carriers such as diatomaceous earth, alumina, bauxite, pumice stone, silica alumina, activated carbon, etc. Typical examples of these catalysts are nickel-carrying diatomaceous earth, molybdenum-carrying alumina, platinum-carrying alumina, cobalt-carrying alumina, etc. The reaction is carried out under the following conditions: a temperature of lO0-450 C, a pressure of 10-300 kg/cm, a feed rate of hydrogen of 5-30 moles per mole of alkylated tar and a liquid hourly space velocity of 0.5-10 cc/cc-catalyst/hr. The reaction in this step involves mainly the hydrogenation of the polycyclic aromatic compounds not accompanied by such side reactions as the dissociation of the alkyl side chain, the ring opening of the naphthene rings, decomposition, polymerization, etc., thus forming alkylated polycyclic naphthene compounds in good yield. By removing fractions having boiling points of lower than 250-300 C, calculated at normal pressure, from the reaction product thus obtained, the vehicle of this invention can be obtained.

The paint vehicle of this invention gives particularly excellent effects as painting materials to resins having three-dimensionally cross-linked structures by curing. As these resins, there may be illustrated the following: alkyd resins, urethane resins, epoxy resins, epoxyurethane resins, alkydurethane resins, esterified epoxy resins, epoxy-alkyd resins, and the like.

By using 5500 parts by weight of the vehicle of this invention to parts by weight of the aforesaid resin, effective water resisting and anticorrosive properties can be obtained. Moreover, in the case of employing expensive resins such as epoxy resins and urethane resins, by using a properly large amount of the vehicle, the cost of the paint may be reduced without degrading the properties of the resin itself. The above-mentioned vehicle, relating to the present invention, may be optionally blended with either prepolymers or hardening agents for the epoxy resin or urethane resin without any trouble.

Furthermore, when a painting material is prepared from the resin and the vehicle of this invention, a solvent may be used for facilitating the painting operation. As such a solvent, there are illustrated aromatic, aliphatic and alicyclic hydrocarbons; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; esters such as ethyl acetate, amyl acetate, etc.; cyclic ethers such as tetrahydrofuran, dioxane etc.; and chlorine-containing compounds such as carbon tetrachloride, ethylene dichloride, etc. These solvents may be used alone or as mixtures thereof according to the purpose and uses thereof.

The vehicles of this invention may further be modified by adding various conventional additives such as a plasticizer, a softening agent, a filler, a curing agent, a curing accelerator, an antioxidant, a colorant,

etc.

The invention will now be explained further by referring to the following examples, which are deemed to be merely illustrative, and not limiting, in nature.

EXAMPLE 1 I Nucleus hydrogenation Ni-diatomaceous earth (by weight) Desulfurization Co-Ni-alumina Reaction alkylation Catalyst silicaalumina I (by weight) 3:7:90 (by weight) pressure kglcm gauge temperature liquid hourly space velocity (cc/cccatalyst/hr) butylene/raw material (mole ratio) hydrogen/raw material (mole ratio) butylation degree (mol/mol-tar) The general properties of vehicle A thus obtained were as follows:

Specific gravity Softening point NMR aromatic C--H proton density 0 Visible percent transmittance of hexane solution at 500 mp Mean molecular weight (VPO) The NMR spectrum of vehicle A is shown in FIG. 1

of the accompanying drawings. Also, the percent transmittance is shown in FIG. 3 as curve 1.

EXAMPLE 2 sure, the vehicle B of this invention was obtained.

Reaction desulfurization alkylation silica- Nucleus hydrogenation Catalyst Co-Mo-alumina Ni-alumina (by weight) :15 (by weight) pressure (kglcm -G) temperature liquid hourly space velocity (cc/cccatalyst/hr) ethylene/raw material (mole ratio) hydrogen/raw material (mole ratio) 5 ethylation degree (moles/moles -bottom oil) The general properties of vehicle B are as follows:

Specific gravity 0.975

Viscosity 4,500 cps NMR aromatic C-H proton density 0.5

Visible ercent transmittance of IO% exane solution at Mean molecular weight (V.P.O.) 380 EXAMPLE 3 A bottom oil obtained from a low-severity ethylene cracking of petroleum naphtha was subjected to desulfurization and nucleus hydrogenation under the conditions shown in the following table. By removing fractions having boiling points of lower than 380C, calculated at normal pressure, vehicle C of this invention was obtained.

Reaction Desulfurization nucleus hydrogenation Catalyst Co-Ni-alumina Ni-diatomaceous earth 3:7:90 (by weight) 40:60 (by weight) pressure (kglcm*-G) 50 temperature liquid space velocity (cc/cc-catalyst/hr) 0.5 1.0

hydrogen/raw material (mole ratio) 5 10 The general properties of vehicle C of this invention T e abo e test was made according to JlS-K-5400. re ared above are as follows: p p EXAMPLE Specific gravity 0965 Each of vehicles A, B and C prepared in Examples 1, x' f g gg OH proton cps 5 2 and 3, respectively, was blended with an alkyd re sin density 1.0% (as shown below) and the properties of the painting Vlslble material thus prepared were investigated. in the test of hexane solution at 500 mp. 98% procedures, the painted material having the following Mean molecular weight tVPO) 330 10 composition was l d EXAMPLE 4 Composition 3 Each of vehicles A, B and C of this invention pr p r in E p 2 and respectively. was Vehicle of the present invention I00 parts(by weight) blended in an epoxy resin to provide a painting material l5 vecowl (made y Nippon d h h T bl 1 d t d reichhold) 100 parts(by weight) an t e tests s own in a e were con uc e using Mixture ofcobalmaphthenm the painting material thus prepared. The compositions and manganese naphthcnate 5 Elam 2 Test method "a b c d e t g One year Compoindistilled Fade-O-meter, Outdoor exposure Vehicle sitlon Water 2,000 hrs. for 1 year mandrel 100/100 Du Pont type, 0.6 kg.-"0 cm. (:11

A 3 Unvarled Not interior to con- Not inferior to con- Endured. Passed. Neither cracked nor stripped by the im- H trol sample. trol sample. pact of the Weight. B 3 do do .do do do do H C 3 ..do do do do do do H "a=water resistance; b=light tastness; c=weathering resistance; d=bending resistance; e=adhesion test; i=impact resistance; g=hardness.

of the painting materials used in the tests were as follows:

Composition 1 Vehicle of the present invention I00 parts(by weight) Epicoat lOOl (made by Shell The properties of the painted material after baking are shown in Table 2, and as shown in the table, they were very excellent.

The above test was made according to 11$ K-5400.

EXAMPiLE H5 (made b She" 66 Each of vehicles A, B and C prepared in Examples 1, Chemical) y 34 2 and 3, respectively, was blended with a urethane resin Methyl isobutyl Ketone 60 (as shown below) to provide a urethane resin painting Composition 2 material. The composition of the painting material is as follows:

Vehicle of the present invention 100 parts(by weight) if "A Epicoat 828 (made by Shell Composmon 4 Chemical) 200 parts(by weight) W Diethylene triamine 26 I Vehicle of the present gags" dlmethylammomethyl) 2 iglventio l 000 (M 100 parts(by weight) ester itsui Dloctyl phthalate l0 Toatsuxagaku Co) u The properties of the painted material after baking 50 gg 90 are shown in Table 1. Ethyl acetate 5 TABLE 1 Test method "a b c d e t g One year Compoin distilled Fadeb-meter Outdoor exposure W Vehicle sition Water 2,000 hrs. for 1 year mandrel I00/100 Du pont type, 1 kg. cm. Pencil 1 Unvaricd..- No change in color No change in color Endured Passed.. Neither cracked nor stripped 2 11-11 by the im act of the Wei ht. do do do p g a=water resistance; b=light iastness; c=wcathering resistance;

d bending resistance; o= adhesion test; i= impact resistance; g= hardness The properties of the painted material were meadetermined by nuclear magnetic resonance absorption sured, the results'of which are shown in Table 3. As is spectrum, and a transparency such that the percent clear from the results, the prepared painted materials transmittance of a percent hexane solution thereof, showed excellent properties, measured by the absorption of visible light of 3155 MW. WWW

Test method "a b c d e i g One year Compoindlstilled Fade-O-meter Outdoor exposure Vehicle sltion water 2,000 hrs. for 1 year. mandrel 100/100 Du Pont type, 1 kg.-50 cm. Pencil A 4 Unvaried. N 01; inferior to con- Not inferior to con- Endured.. Passed Neither cracked nor stripped by the impact 2H-H trol sample. trol sample. of the weight B 4 do ..do ..d0 do .do ..do 211 C 4 do do .do d0 ..do-- do H '*a=water resistance; b=light fastness; c=weathering resistance; Norm-The above test was made according to J 18 K-5400.

d=bending resistance; e=edhesion test; f=impact resistance; g=hard- HESS.

What is claimed is: wavelengths longer than 500 mg, is higher than 60 per- 2 cent wherein the softening point of said vehicle varies from to 100 C as a solid and wherein the viscosity of said vehicle as a liquid at 25 C varies from 1,000 to 50,000 cps.

2. The paint vehicle of claim 1, wherein said percent 25 transmittance is hlgllef than 80 per cent.

l. A paint vehicle comprising a hydrocarbon compound having a specific gravity of from 0.92 to 1.0, a mean molecular weight of from 200 to 1,000 measured by a vapor pressure osmotic pressure method, an aromatic CI-l proton density of less than 3 percent, said aromatic CH proton having a value of less than 4 

1. A paint vehicle comprising a hydrocarbon compound having a specific gravity of from 0.92 to 1.0, a mean molecular weight of from 200 to 1,000 measured by a vapor pressure osmotic pressure method, an aromatic C-H proton density of less than 3 percent, said aromatic C-H proton having a value of less than 4 determined by nuclear magnetic resonance absorption spectrum, and a tranSparency such that the percent transmittance of a 10 percent hexane solution thereof, measured by the absorption of visible light of wavelengths longer than 500 m Mu , is higher than 60 percent wherein the softening point of said vehicle varies from 25* to 100* C as a solid and wherein the viscosity of said vehicle as a liquid at 25* C varies from 1,000 to 50,000 cps. 